WO2013153103A1 - Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse - Google Patents
Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse Download PDFInfo
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- WO2013153103A1 WO2013153103A1 PCT/EP2013/057470 EP2013057470W WO2013153103A1 WO 2013153103 A1 WO2013153103 A1 WO 2013153103A1 EP 2013057470 W EP2013057470 W EP 2013057470W WO 2013153103 A1 WO2013153103 A1 WO 2013153103A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/186—Regeneration by electrochemical means by electrolytic decomposition of the electrolytic solution or the formed water product
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
- H01M8/222—Fuel cells in which the fuel is based on compounds containing nitrogen, e.g. hydrazine, ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- Electrolytic fuel cell device circulating through percolation through porous three-dimensional structure electrodes
- the present invention relates to a particular circulating electrolyte fuel cell device, and to its various applications in the transport sector and the stationary sector.
- Electrochemical generators are usually classified into three classes: batteries, accumulators and fuel cells. All possess the property of transforming the chemical energy provided by a redox reaction into electrical energy.
- an electrochemical generator comprises two electrodes bathed in an electrolyte solution and optionally a separator that can take the form of an electrochemical bridge or a membrane permeable to the ions of the support electrolyte.
- a separator that can take the form of an electrochemical bridge or a membrane permeable to the ions of the support electrolyte.
- At the terminals of each of these electrodes is an oxidation reaction and a reduction reaction respectively, involving one of the reactants of the oxidation-reduction reaction at the origin of the operation of the generator.
- Anode is the electrode in which the oxidation reaction occurs which will release electrons and corresponds to the negative terminal of the generator.
- the cathode is the electrode where the reduction reaction occurs and corresponds to the positive terminal of the generator.
- the current delivered is proportional to the concentration of the species brought into contact electrodes.
- Electric batteries also referred to as batteries, or primary generators, operate in a closed system and discharge their electrical energy without the possibility of returning to their original state. In other words, once the electroactive species of the oxidation-reduction reaction are exhausted, the cell can not be recharged and needs to be replaced.
- Accumulators or secondary generators are also closed systems but on the other hand, reversible, that is to say they are capable of being recharged electrically after discharge if they are provided with external electrical energy, for example through another generator.
- Accumulators are designed to withstand many charge / discharge cycles. In discharge mode, it functions as an electric battery, in charge mode, it functions as an electrolyser. In the latter case, the electroactive species of the oxidation-reduction reaction consumed during the flow of the cell are then regenerated and can be reused. However, the energy capacity of the accumulators remains limited by the volume of the system.
- Fuel cells have the advantage of being open systems. Their capacity is therefore not limited by such a limitation of volume. Fuel cells can work:
- electrolytic solution is called a solution comprising as solute at least one electrolyte.
- Electrolytes are ions that promote the flow of current (Na + , sulfate, H + , OH-, ...) in the electrolytic solution.
- electrolytes are those ions that actively participate in the current transport.
- An electrolytic solution is therefore electrically conductive.
- the electrolytes can be obtained for example by dissolving a salt corresponding to a combination of cations and anions in the solvent of the electrolytic solution.
- the electrolytic solutions may further comprise an oxidant or a reducing agent.
- Anolyte is defined as the electrolytic solution containing in addition at least one electroactive species acting as a reducing agent.
- the electrolyte solution is defined by catholyte additionally containing at least one electroactive species acting as an oxidizer.
- the electroactive species required at the electrodes are stored in storage compartments (tanks) located outside the electrochemical reactor, headquarters of oxidation-reduction reactions.
- storage compartments tanks located outside the electrochemical reactor, headquarters of oxidation-reduction reactions.
- the capacity of the fuel cell no longer depends on its own volume but the volume of the storage compartments, while the power of the fuel cell remains related to the size of the reactor.
- the decoupling of these two parameters is an advantage for the massive storage of energy in networks. To do this, it is important to have sufficient tanks, while the independence from the power is conditioned by the intended use.
- the power of the fuel cell can be modulated according to the size of the electrochemical reactor. Indeed, the latter may consist of one or more cells connected in parallel or in series so as to obtain the intensity of the current or the desired electromotive force.
- Each cell comprises at least one anode, a cathode, and an electrolytic solution comprising at least one oxidant and / or reducing agent, and is capable of producing electricity from a redox reaction.
- the power of the stack obtained depends on the number of cells assembled and their surface. A wide power range from kilowatt (kW) to several megawatts (MW) can be achieved. In addition, there are a large number of redox couples that can be involved in each cell.
- Another advantage of circulating electrolyte fuel cells is the ability of the system to operate continuously. When the electroactive species involved in the oxidation and reduction reactions are exhausted near the electrodes, they are continually replaced by the circulating flow of the electrolytic solutions. The system is therefore rechargeable without the need to interrupt power generation.
- Circulating electrolyte fuel cells have many advantages as mentioned above.
- the existing systems are not entirely satisfactory in terms of electrical and energy efficiency and remain to be improved.
- the recharge time after depletion of electroactive species is often a brake for long-term use (for example of the order of several days) and harms the continuous and homogeneous generation of electricity.
- the regeneration of at least one electroactive or oxidizing electroactive species requires several passes of the electrolyte solution in the cell to the contacts of the electrodes. This obligation entails an additional cost of energy resulting from the faradic efficiency of the electrolysis and the excessive operation of the pumps.
- the diversity of redox systems used in existing circulating electrolyte systems is very low and consists mainly of some elements of the periodic table of the family of metals (vanadium, zinc and iron) and the family of halogens (bromine and chlorine).
- the problem to be solved by the present invention is to develop an electrochemical generator to overcome these disadvantages, while retaining the advantages of existing circulating electrolyte fuel cells.
- the present application aims to obtain an electrochemical generator, capable of generating electrical energy continuously or support other sources of intermittent energy, store and reuse on demand of electrical energy quickly and therefore rechargeable quickly.
- the invention thus relates to a rechargeable circulating electrolyte fuel cell device as defined below.
- the device according to the invention is rechargeable, capable of generating or co-generating, storing, reusing on demand electrical energy.
- t represents the time of optimization of the electromotive force and the intensity of the current of the circulating electrolyte fuel cell (mn), t represents the time necessary to move a volume V
- V represents the volume of each electrode (dm 3 )
- d represents the flow rate of the electrolytic solutions (dm 3 / min).
- t R represents the recharge time (mn)
- V R represents the volume of the tank (dm 3 )
- d represents the flow rate of the electrolytic solutions (dm 3 / min).
- the recharge rate of the device according to the invention preferably varies between 95 and 100% in a single passage of the electrolytic solution (anolyte, catholyte) throughout the circuit of the device, and more precisely a single passage of the entire volume. of the electrolytic solution through the electrode.
- the device according to the invention has a high electrical efficiency independent of the size of the electrochemical reactor.
- the electrodes of the device according to the invention through which percolate electrolytic solutions have increased mechanical properties compared to conventional electrodes do not allow electrolytic solutions to percolate through.
- the subject of the invention is a circulating electrolyte fuel cell device comprising:
- At least one cell having a positive compartment provided with an anode and a negative compartment provided with a cathode, said compartments being separated by an ion-permeable membrane;
- At least one first pump for circulating the catholyte in a circuit comprising the catholyte reservoir, the first catholyte supply line in the positive compartment, the positive compartment and the second catholyte discharge line;
- At least one second pump allowing the circulation of anolyte in a circuit comprising the anolyte reservoir, the first feed line for the panolyte in the negative compartment, the negative compartment and the second anolyte discharge line;
- the positive compartment comprising a positive downstream compartment and a positive upstream compartment separated by the anode
- the first catholyte supply pipe being connected to said positive upstream compartment and the second catholyte discharge pipe being connected to said positive downstream compartment
- the negative compartment comprising a negative downstream compartment and a negative upstream compartment separated by said cathode, the first anolyte supply pipe being connected to said negative upstream compartment and the second anolyte discharging pipe being connected to said compartment; negative downstream,
- catholyte and anolyte being able to pass through percolation respectively through said anode and said cathode;
- the electro-lyric solution (catholyte, anolyte), to pass from the downstream compartment to the upstream compartment, must percolate through the electrode (anode, cathode).
- the electrode anode, cathode.
- the characteristic according to which the catholyte and anolyte solutions pass through the electrodes in a flow orthogonal to the longitudinal axis of these latter makes it possible to avoid, during this percolation, too great a pressure within the three-dimensional porous materials constituting those -this.
- the longitudinal axis of the electrodes is the one passing through their largest dimension (length or height or diameter). In practice, these electrodes have a flat shape and a small thickness. They may in particular be in the form of parallelepipeds.
- the cathode and / or anode used in the device according to the invention may be made of a material selected from the group consisting of foams, felts, fabrics or fabric overlays. Preferably, felt is used.
- the cathode and / or the anode used in the device according to the invention is (are) thus preferably made (s) of carbon fiber felt, and more preferably in graphite fiber felt. Graphite is preferred because it has a higher electrical conductivity than carbon.
- graphite fibers include those marketed by Mersen or Pica. There are two available thicknesses available: 12mm marketed by Mersen under the reference RVG 4000 and 6mm corresponding to the RVG 2000. Apart from the thickness, these materials are exactly the same. These felts consist of an entanglement of graphite fibers. The very high porosity of the felt is difficult to quantify and corresponds more to spaces between fibers, of greater or lesser size, rather than to pores of well-defined diameter.
- the apparent surface evaluated by Mersen (by the so-called BET method) is 0.7m 2 . g -1 .
- the overall appearance of each fiber whose average diameter is between 20 and 25 microns is very homogeneous appearance.
- These fibers, whose manufacture is unique to Mersen, are obtained by pyrolysis of an acrylic base polymer.
- the pens offered by the company Pica are also marketed in roll, but with a maximum thickness of 0.3 cm.
- One of the markers marketed by Pica is characterized by a very large surface area of 1200m 2 . g -1 , measured, according to Pica, by the BET method, which corresponds to a surface approximately 1700 times larger than the Mersen graphite felts. This is because the average fiber diameter is small, about 10 microns and the fiber density is high.
- the cathode and / or the anode are made of graphite fiber felt, they may be used as such or modified by one or more the following preparation methods:
- a cyclic organic complex comprising at least one primary or secondary amine function, such as an optionally substituted phthalocyanine metal complex, or optionally substituted porphyrin, such as an iron complex, cobalt, copper, nickel or noble metal, or a phenazathionium (or methylene blue) or a substituted phenazathionium.
- polymer that can be used for the preparation method c) defined above it is possible to choose for example a polymer of the family of polypyrroles, the family of polythiophenes, the family of polyanilines, the family of ethylenedioxythiophenes (EDOT).
- a polymer of the family of polypyrroles or polythiophenes Preferably, a polymer of the family of polypyrroles or polythiophenes.
- the cathode and / or the anode are made of graphite fiber felt, they can be used as such or metallized.
- they may also, alternatively, be coated with a polymer.
- a catalyst may also be covalently attached to the surface of said cathode and / or said anode.
- the process for covalently bonding one or more catalysts may be carried out directly on at least one of the graphite fiber felt surfaces of the cathode or anode, or directly on the polymer film attached to the optionally metallized graphite fibers.
- the covalent attachment method can be carried out for example by electrochemical reduction of a diazonium salt.
- the method consists in generating in solution a diazonium salt derived from the corresponding amine of the catalyst.
- the diazonium salt is then reduced electrochemically to the electrode.
- the reduction leads to the formation of a radical carbon which binds covalently to the surface of the electrode. This reaction is accompanied by a release of N 2 .
- Another method is to incorporate one or more catalysts into the structure of a polymer thereby rendering it electroactive.
- the fixing of one or more catalysts as defined above can be carried out on at least one of the graphite fiber felt surfaces previously coated with an electroactive polymer film of the cathode or the anode.
- the coating of the electroactive film around the graphite fibers is achieved by "electropolymerization" of a monomer. There are many monomers such as: aniline, pyrole, thiophene ... etc.
- Electropolymerization is an electrochemical technique which in oxidation makes it possible to generate radicals derived from the monomers and which will bond with each other to form a conjugated polymer.
- the catalyst (s) is blocked on the surface of the electrode by the formation of the polymer.
- the electropolymerization thus makes it possible to coat the surface of the felt electrode with graphite fibers with a polymer film incorporating one or more catalysts.
- the cathode and the anode can be made of identical or different materials.
- a cathode and / or anode made of graphite fiber felt of entirely metallized graphite fiber felt optionally coated on at least one of its surfaces with a film.
- polymer on which is or is optionally covalently attached one or more catalysts graphite fiber felt coated on at least one of the surfaces of a polymer film on which is or are optionally covalently attached or incorporated one or several catalysts.
- Metallic graphite fiber felt electrodes are preferably used.
- the electrodes used according to the invention are not limited as to their shape or their thickness. Preferably, they have a thickness greater than 0.3 cm. More preferably, they have a thickness of up to 1.2 cm.
- Each electrode may be positioned parallel to the plane of the ion-permeable membrane or perpendicular to it.
- all the electrodes are positioned parallel to the plane of the membrane permeable to ions. This configuration provides a compact cell and thus a space-saving device.
- the electrodes used in the device according to the invention have both a high specific surface area and a high microporosity, which presents an advantage for the miniaturization of electrochemical generators.
- the graphite fibers can be obtained by pyrolysis of a base polymer of acrylic type.
- the metallization of the graphite fibers of the cathode and / or of the anode can be carried out by electrodeposition by a process as described for example in the patent application FR2846012.
- the electrolytic solutions that can be used in the device according to the invention are liquid fluids containing ions called carrier electrolytes, further containing at least one oxidant or at least one reducing agent.
- the part of the electrolyte solution containing the reductant in contact with the anode of one or the negative compartment of the fuel cell device according to the invention is called anolyte.
- the part of the electrolyte solution containing the oxidant in contact with the cathode of a positive compartment or compartment of the fuel cell device according to the invention is called catholyte.
- the anolyte is an electrolytic solution comprising at least one reducing agent.
- the catholyte is an electrolytic solution comprising at least one oxidant.
- the liquid fluid generally employed as a solvent for electrolytic solutions is generally an aqueous solution (water), which can be acidic, basic or neutral.
- the anolyte and the catholyte are aqueous solutions of the same nature (acid, basic, or neutral).
- an aqueous electrolyte solution comprising at least one reducing agent is used as the anolyte.
- the reducer undergoes a spontaneous oxidation reaction in the negative compartment at the anode when the device generates current (battery operation).
- alcohols of low molecular weight such as C 1 -C 4 alcohols, such
- an aqueous electrolyte solution comprising at least one oxidizing agent is used as catholyte.
- the oxidant undergoes a spontaneous reduction reaction in the positive compartment at the cathode when the device generates current (battery operation).
- ferricyanide / ferrocyanide corresponding respectively to a complex salt containing the trivalent Fe (CN) 6 3 ion and to a complex salt containing the tetravalent Fe (CN) 6 ion.
- organic oxidants such as catechol derivatives and quinones, in particular hydroquinones, organometallic oxidants based on, for example, cyclam derivatives, metal complexes of iron (Fe / Fe) or cobalt ( Co / Co) with one of the phenanthroline ligands, citric acid or ethylene diamine tetraacetic acid (EDTA), and Ce 4+ / Ce 3+ ; ferrocene and substituted ferrocenes; metal-based systems, such as for example vanadium; oxygen.
- the preferred oxidant is ferricyanide, especially potassium ferricyanide. The latter coexists in aqueous solution with ferrocyanide.
- Cyclamines complexed with transition metals can advantageously be used as circulating electrolytes.
- cyclam 1,4,8,11-tetraazacyclotetradecane, called "cyclam” is part of the family of tetraazacycloalkanes.
- the cyclam shown below comprises four nitrogen atoms placed in a symmetrical configuration.
- the cyclam complex all the elements of transitions M and this at varying degrees of oxidation.
- Cyclam complexes have one or two electrochemical systems depending on the nature of the metal cation.
- Cyclame (Ni) has two redox systems, one of which is located at low potential and the other at high potential.
- cyclams as electrolytes has the advantage of not generating problem if a mixture of anolyte and catholyte occurs by passing through the battery membrane.
- the molar reducer concentration and the molar concentration of oxidant present in the or each cell of the device according to the invention, in the anolyte and the catholyte, are preferably chosen so as to obtain the electromotive force and the intensity, and therefore the desired power.
- the electromotive force of the fuel cell device is defined by Nernst's law.
- the current delivered is proportional to the molar concentration of reductant in the positive compartment, and to the molar concentration of oxidant in the negative compartment of each cell or cell of the device.
- the device according to the invention may consist of one or more cells connected in parallel or in series. This arrangement makes it possible in particular to obtain an increased electric power.
- the ion-permeable membrane of the carrier electrolyte used in the device according to the invention separates the anolyte from the catholyte and prevents any contact between the reductant contained in the anolyte and the oxidant contained in the catholyte.
- the membrane is selected to withstand the oxidizing environment of the anode and reducing the cathode.
- the membrane is preferably chosen to promote the passage of the ions of the support electrolyte, and in particular protons (H + ) and / or hydroxyls (OH) present and / or generated in the anolyte and the catholyte. , through the membrane so as to minimize the electrical resistance of the membrane.
- the membrane used is a membrane permeable to at least one common ion present in the catholyte and the anolyte.
- the membrane used is permeable to protons and hydroxyls.
- the membrane used is permeable to protons (H + ) when the anolyte and the catholyte are acidic solutions.
- the membrane used is permeable to hydroxyls (OH " ), when the anolyte and the catholyte are basic solutions.
- pump (s) ensuring the circulation of the catholyte and anolyte in the device according to the invention contributes to facilitate the passage of these fluids through the anode and the cathode respectively.
- the pump (s) used are those conventionally used for conventional fuel cells. For example, peristaltic pumps may be used.
- the location of the pumps in the device is not critical provided that they perform their function of circulating electrolytes.
- the reservoir of an anolyte comprises said anolyte.
- the reservoir of a catholyte comprises said catholyte.
- the size of the reservoirs used in the device according to the invention is preferably chosen as a function of the energy requirement of the applications developed and the desired autonomy: systems with a low amount of energy (portable device), with a medium energy requirement (vehicle ) or with a high energy requirement (residential or buildings for heating, cooling or power supply). It can also depend on the concentration of active species (oxidant (s) / reductant (s)) in each tank.
- the device according to the invention comprises at least one system for recycling and / or enriching the electrolytic solutions for replenishing and / or enriching the anolyte and catholyte reservoirs with active species (reducing agent and oxidant respectively) .
- Each recycling system is placed between the outlet of the electrolyte drain pipe and the inlet pipe of the electrolyte tank.
- Recycling can be obtained by simply reintroducing the unreacted active species into the reservoirs (recirculation of the output electrolyte solutions).
- the enrichment of active species can be obtained by an electrochemical reaction opposite to that taking place in the electrochemical cell.
- the enrichment of the electrolyte solutions can be carried out advantageously by closed loop electrolysis using the same electrodes (electrochemical cells) of the circulating electrolyte fuel cell device.
- an electric current of an external source is imposed on the terminals of the electrodes of the fuel cell.
- the flow direction of the electrolytes passing through the electrodes of porous three-dimensional structure is the same as in the energy production mode and thus retains the advantage of a passage of the electrolyte from the membrane towards the electrodes.
- the anolyte reservoir may also be enriched, for example by 1,2,4,5-tetraol benzene by subjecting the oxidized reductants recovered at the outlet of the electrochemical cell, to a reduction reaction (for example by electrolysis).
- the tank of the catholyte may also be enriched, for example potassium ferricyanide by subjecting the reduced oxidants recovered at the outlet of the electrochemical cell, an oxidation reaction (for example by electrolysis or oxidation with the aid of dioxygen).
- the reducer concentration in the anolyte reservoir may thus be different from that present in the negative (anode) compartment of the cell.
- the concentration of oxidant in the catholyte reservoir may be different from that present in the positive (cathodic) compartment of the cell.
- the reducer concentration in the anolyte reservoir may be greater than or equal to the reducing concentration in the anode compartment.
- the oxidant concentration in the catholyte reservoir may be greater than the oxidant concentration within the cathode compartment.
- the energy content of these reservoirs can be regenerated by electrolysis (inversion of the operation of the cell), for example by applying electrical energy directly at the electrodes.
- the device according to the invention operates as a battery with two modes of operation called “charge” (electrolysis) and “discharge” (battery). In “charge” mode, the oxidation-reduction reactions that take place in the positive and negative compartments of the cell or of each cell in the recharge mode of the device, are the reverse of those occurring in battery operation.
- the active species previously described as reducing agent undergoes a reduction reaction in the positive compartment at the anode, while the active species previously described as oxidant undergoes an oxidation reaction in the negative compartment at the cathode.
- 1,2,4,5-tetraol benzene as reducing agent, in the place of irreversible reducing agents, such as hydrazine whose irreversible oxidation reaction leads to the formation of dinitrogen.
- the electrical energy used to carry out electrolysis of the active species is provided by means of a free external energy source (sun, wind, tide, cascade, deceleration, etc.) converted into electrical energy.
- a free external energy source unsun, wind, tide, cascade, deceleration, etc.
- said membrane is juxtaposed to the cathode and to the anode, that is to say that no compartment is formed between the membrane and the electrodes.
- the circulation of the catholyte is implemented in the direction from the membrane to the anode and the flow of the anolyte is carried out in the direction from the membrane to the cathode respectively.
- the device comprises a flow distribution plate anolyte and a catholyte flow distribution plate.
- said catholyte and said anolyte comprise irreversible reductant and oxidant.
- said catholyte and said anolyte comprise reversible reductant and oxidizer, the device thus being capable of operating in discharge mode, and in charge mode by apposition of an electric current from an external source to the terminals of the anode and the cathode.
- the device according to the invention can be used for various applications in the transport sector (electric vehicle) and the stationary sector (residential or buildings for heating, air conditioning or power supply).
- FIGS. 1 to 5 Five embodiments of devices according to the invention have been realized. These embodiments are schematically represented in FIGS. 1 to 5. The first embodiment, diagrammatically shown in an exploded view in FIG.
- a cell composed of a positive compartment (10) and a negative compartment (20);
- each porous electrode (1) and (2) respectively, defining positive upstream / downstream compartments (10a, 10b) and negative upstream / downstream compartments (20b, 20a) and all identical: 5mm thick and 7.5cm internal diameter.
- the difference in the internal diameter between the porous electrode and the rings makes it possible to simply hold the electrode during the circulation of the fluid.
- Each ring (11, 12, 13, 14) is crossed by a pipe (la, 12a, 13a, 14a) presenting a outer diameter of 3mm.
- Each ring thus has two openings (external and internal) corresponding to an inlet and outlet electrolytic solution, or vice versa:
- the rings (11,13) pressed against the membrane (3) are each traversed by a pipe (la la; 13a) located down in Figure 1, corresponding to the entry of the electrolyte solution (anolyte or catholyte) in the electrochemical cell.
- the rings (12,14) pressed against the two external support plates (15,16) of the device are traversed by a pipe (12a; 14a) located upwards in FIG. 1, corresponding to the outlet of the electrolytic solution ( anolyte or catholyte) outside the electrochemical cell.
- the design of the cell is symmetrical.
- the positive and negative compartments have the same arrangement.
- the pipe (l ia; 13a) passing through its thickness the ring pressed against the membrane (3) is positioned so as to be at the bottom of the cell.
- the pipe (12a; 14a) extending through its thickness the ring (12; 14) pressed against the external support plate of the device is positioned to be at the top of the cell.
- the electrolytic solution fills the compartment and leaves the top of the cell to be discharged into the receiving tank;
- An electrolytic solution common to the anolyte and the catholyte namely an aqueous solution of sodium hydroxide (NaOH) to one mole per liter;
- a reducing agent namely hydrazine at 0.2 mol / l in the anolyte
- an oxidant namely potassium ferricyanide at 0.8 mol / l in the catholyte.
- the cell has a positive compartment (10) provided with the anode (2) and a negative compartment (20) provided with the cathode (1). These compartments are separated by the membrane (3) permeable to hydroxyl ions.
- the tank (5) of the catholyte is provided with a first conduit (5a) for feeding the catholyte into said positive compartment, this first pipe (5a) being connected to the pipe (11a), and a second pipe ( 5b) evacuation of the catholyte of said compartment positive, this second pipe (5b) being connected to the pipe (12a).
- the first pump (7) allows the circulation of the catholyte in a circuit comprising the catholyte reservoir (5), the first catholyte supply line in the positive compartment, the positive compartment and the second catholyte discharge line.
- the reservoir (4) of the anolyte is provided with a first pipe (4a) for feeding said anolyte into said negative compartment, this first pipe (4a) being connected to the pipe (13a), and a second pipe (4b) discharging said anolyte said negative compartment, this second pipe (4b) being connected to the pipe (14a).
- the second pump (6) allows the circulation of the anolyte in a circuit comprising the anolyte reservoir (4), the first anolyte feed line in the negative compartment, the negative compartment and the second conduit. evacuation of the anolyte.
- each electro-lyric solution (anolyte or catholyte) is forced through the corresponding porous electrode (anode or cathode).
- said positive compartment (10) comprises a positive downstream compartment (10a) and a positive upstream compartment (10b) separated by said anode (2), the first catholyte supply pipe being connected to said positive upstream compartment and said second catholyte discharge line being connected to said positive downstream compartment; and said negative compartment (20) comprises a negative downstream compartment (20a) and a negative upstream compartment (20b) separated by said cathode (1), the first anolyte supply pipe being connected to said negative upstream compartment and said second the anolyte evacuation line being connected to said negative downstream compartment; said catholytes and anolytes passing through percolation respectively through said anode and said cathode, according to orthogonal flows.
- the discharge rate corresponds to the calculation of the percentage of the quantity of electricity used, calculated from the theoretical load of 772000 Coulomb, and reflects the depletion of the hydrazine anolyte and the ferricyanide catholyte.
- the operating time of 8.5 hours corresponds to the passage of ten liters of electrolyte in the cell. Beyond this time and given the low depletion of hydrazine in the anolyte and ferricyanide in the catholyte, these two solutions are returned to their initial reservoir respectively (4) and (5) and the flow system is looped.
- the device according to the invention has a high energy capacity to consider its use in stationary systems spans, that is to say in residential or buildings for heating, air conditioning or supply current. Connected in parallel, several cells of the device according to the invention can lead to the intensity of the desired current or connected in series to the f.e.m. desired.
- the amount of electricity is 772 x 10 6 Coulomb.
- This large amount of electricity can be distributed in a high form in current intensity or potential difference (ddp) for several days.
- the system is then easily integrated into a local energy production process (photovoltaic, wind, etc.) to store energy. In particular, it can play a role in the release of energy by compensating for the non-production in energy of the wind and photovoltaic systems (absence of wind, light)
- the device can be used as an electricity generator for medium-sized electric vehicles, with current consumption ranging from 60 to 80A.
- FIG. 2 discharge
- FIG. 3 discharge mode
- This second embodiment differs from the first embodiment described with reference to FIG. 1 in that: the membrane (3) is juxtaposed with the electrodes (1, 2) without delimiting a compartment between the membrane and the electrodes;
- the anolyte inlet through the pipe (4a) is at the support plate (15) while the catholyte inlet through the pipe (5a) is at the support plate (16);
- the anolyte outlet via the pipe (4b) is at a holding ring (1a) surrounding the porous electrode (1) provided with a pipe (1b) passing through it and connected to the pipe (4b) while the catholyte outlet is at a holding ring (2a) surrounding the porous electrode (2) provided with a pipe (2b) therethrough and connected to the pipe (5b);
- the rings (12b, 14b) delimiting the downstream compartments (20a, 10b) are not provided with pipes passing through them; the current is received by conducting rings (17, 18).
- the third embodiment carried out is described with reference to FIG. 4, in which the reservoirs of the anodic and cathodic solutions, as well as the regeneration and enrichment loops thereof, are also not represented.
- This third embodiment differs from the first embodiment described with reference to FIG. 2 in that: the anolyte inlet through the pipe (4a) is via the pipe (1b), the anolyte outlet through the pipe (4b) being made by the retaining ring (15); the catholyte inlet through the pipe (5a) is through the pipe (2b), the catholyte outlet through the pipe (5b) is through the retaining ring (16).
- This third embodiment therefore differs from the second embodiment in the flow direction of the electrolytic solutions.
- This third embodiment differs from the first embodiment described with reference to FIG. 2 in that: a distribution plate (19) is provided between the ring (12b) and the electrode (2) and another plate distribution (21) is provided between the ring (14b) and the electrode (1). These distribution plates are pierced with holes on two-thirds of their height, the upper third thus constituting an obstacle to the passage of electrolyte solutions; a solid plate (30) Teflon ® cooperates with each of the rings (14b and 12b) so as to fill the upper third compartment delimited by it.
- the fifth embodiment realized is described with reference to FIG. 6, in which the reservoirs of the anodic and cathodic solutions, as well as the regeneration and enrichment loops thereof, are also not represented.
- This third embodiment differs from the first embodiment described with reference to FIG. 4 in that: the distribution plates are pierced with holes on two-thirds of their height, the lower third therefore constituting an obstacle to the passage of electrolyte solutions; a Teflon ® plate cooperates with each of the rings (14b and 12b) so as to fill the lower third of the compartment delimited by it; the anolyte inlet through the pipe (4a) is through the pipe (1b), the anolyte outlet through the pipe (4b) being through the retaining ring (15); the catholyte inlet through the pipe (5a) is through the pipe (2b), the catholyte outlet through the pipe (5b) is through the retaining ring (16).
- This fifth embodiment thus differs from the fourth embodiment in the flow direction of the electrolytic solutions.
- the second embodiment has also been tested in battery mode by replacing potassium hydrazine and ferricyanide, irreversible reducing agents and oxidants, by the following compounds:
- 1,2,4,5-tetraol benzene is obtained by electrochemical reduction, directly in contact with the electrodes, 2,5-Dihydroxy- [1,4] benzoquinone, which is a product available in trade.
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13717241.7A EP2837051A1 (fr) | 2012-04-10 | 2013-04-10 | Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse |
CN201380026561.2A CN104380509A (zh) | 2012-04-10 | 2013-04-10 | 具有通过渗滤流经多孔三维结构电极的电解液的燃料电池设备 |
CA2868486A CA2868486A1 (fr) | 2012-04-10 | 2013-04-10 | Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse |
US14/391,895 US20150079497A1 (en) | 2012-04-10 | 2013-04-10 | Fuel cell device with electrolytes flowing by means of percolation through electrodes having a porous, three-dimensional structure |
JP2015504938A JP2015519685A (ja) | 2012-04-10 | 2013-04-10 | 多孔質3次元構造を有する電極を通るパーコレーションによって電解質が流れる燃料電池デバイス |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR1253269 | 2012-04-10 | ||
FR1253269A FR2989225A1 (fr) | 2012-04-10 | 2012-04-10 | Dispositif de pile a combustible a electrolytes circulants, par percolation a travers d'electrodes de structure tridimensionnelle poreuse |
FR1254216A FR2989226B1 (fr) | 2012-04-10 | 2012-05-09 | Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse |
FR1254216 | 2012-05-09 |
Publications (1)
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WO2013153103A1 true WO2013153103A1 (fr) | 2013-10-17 |
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ID=46598747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2013/057470 WO2013153103A1 (fr) | 2012-04-10 | 2013-04-10 | Dispositif de pile a combustible a electrolytes circulant par percolation au travers d'electrodes de structure tridimensionnelle poreuse |
Country Status (7)
Country | Link |
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US (1) | US20150079497A1 (fr) |
EP (1) | EP2837051A1 (fr) |
JP (1) | JP2015519685A (fr) |
CN (1) | CN104380509A (fr) |
CA (1) | CA2868486A1 (fr) |
FR (2) | FR2989225A1 (fr) |
WO (1) | WO2013153103A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109196748A (zh) * | 2016-05-30 | 2019-01-11 | 法国国家科研中心 | 用于通过自主混合站对设备进行供电的方法 |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
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IN2015DN03105A (fr) | 2012-09-26 | 2015-10-02 | Harvard College | |
JP6643983B2 (ja) | 2013-09-26 | 2020-02-12 | プレジデント アンド フェローズ オブ ハーバード カレッジ | キノン及びヒドロキノン系フロー電池 |
FR3052924B1 (fr) | 2016-06-21 | 2019-08-09 | Kemiwatt | Dispositif de protection contre la surcharge electrique pour accumulateur electrochimique |
US11923581B2 (en) | 2016-08-12 | 2024-03-05 | President And Fellows Of Harvard College | Aqueous redox flow battery electrolytes with high chemical and electrochemical stability, high water solubility, low membrane permeability |
US10840532B2 (en) | 2017-01-27 | 2020-11-17 | President And Fellows Of Harvard College | Flow battery with electrolyte rebalancing system |
CN112204789A (zh) | 2018-02-09 | 2021-01-08 | 哈佛大学校长及研究员协会 | 用作水性氧化还原液流电池中的电解质的具有高容量保持率的醌 |
CN110571437A (zh) * | 2018-05-16 | 2019-12-13 | 嘉兴市兆业新能源技术有限公司 | 一种燃料电池的阳极结构 |
US11705571B2 (en) * | 2018-09-05 | 2023-07-18 | Nikolai M. Kocherginsky | Foil-based redox flow battery |
US11557786B2 (en) | 2018-10-01 | 2023-01-17 | President And Fellows Of Harvard College | Extending the lifetime of organic flow batteries via redox state management |
KR102187258B1 (ko) * | 2019-01-03 | 2020-12-04 | 스탠다드에너지(주) | 레독스 흐름전지의 전극 셀 구조 |
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US20050084738A1 (en) * | 2003-10-17 | 2005-04-21 | Ohlsen Leroy J. | Nitric acid regeneration fuel cell systems |
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-
2012
- 2012-04-10 FR FR1253269A patent/FR2989225A1/fr active Pending
- 2012-05-09 FR FR1254216A patent/FR2989226B1/fr active Active
-
2013
- 2013-04-10 WO PCT/EP2013/057470 patent/WO2013153103A1/fr active Application Filing
- 2013-04-10 JP JP2015504938A patent/JP2015519685A/ja active Pending
- 2013-04-10 CA CA2868486A patent/CA2868486A1/fr not_active Abandoned
- 2013-04-10 EP EP13717241.7A patent/EP2837051A1/fr not_active Withdrawn
- 2013-04-10 US US14/391,895 patent/US20150079497A1/en not_active Abandoned
- 2013-04-10 CN CN201380026561.2A patent/CN104380509A/zh active Pending
Patent Citations (7)
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EP0727837A1 (fr) * | 1995-02-16 | 1996-08-21 | Kashima-Kita Electric Power Corporation | Batterie rédox |
EP0814527A2 (fr) * | 1996-06-19 | 1997-12-29 | Kashima-Kita Electric Power Corporation | Batterie redox à circulation |
FR2846012A1 (fr) | 2002-10-18 | 2004-04-23 | Univ Rennes | Dispositif pour metalliser un feutre graphitique, procede mis en oeuvre par ce dispositif, feutre graphitique metallise correspondant et utilisation d'un tel feutre graphitique metallise |
US20050084738A1 (en) * | 2003-10-17 | 2005-04-21 | Ohlsen Leroy J. | Nitric acid regeneration fuel cell systems |
FR2914931A1 (fr) | 2007-04-10 | 2008-10-17 | Univ Rennes 1 Etablissement Pu | Procede de fabrication d'un element de feutre graphitique metallise revetu d'une facon homogene dans tout son volume d'un polymere organique conducteur |
US20090092882A1 (en) * | 2007-10-09 | 2009-04-09 | University Of Victoria Innovation And Development Corporation | Fuel cell with flow-through porous electrodes |
WO2012038379A1 (fr) * | 2010-09-21 | 2012-03-29 | Imperial Innovations Limited | Piles à combustible régénératives |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN109196748A (zh) * | 2016-05-30 | 2019-01-11 | 法国国家科研中心 | 用于通过自主混合站对设备进行供电的方法 |
CN109196748B (zh) * | 2016-05-30 | 2022-04-15 | 法国国家科研中心 | 用于通过自主混合站对设备进行供电的方法 |
Also Published As
Publication number | Publication date |
---|---|
FR2989226B1 (fr) | 2019-12-20 |
US20150079497A1 (en) | 2015-03-19 |
JP2015519685A (ja) | 2015-07-09 |
CA2868486A1 (fr) | 2013-10-17 |
EP2837051A1 (fr) | 2015-02-18 |
FR2989226A1 (fr) | 2013-10-11 |
CN104380509A (zh) | 2015-02-25 |
FR2989225A1 (fr) | 2013-10-11 |
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